U.S. patent application number 14/240804 was filed with the patent office on 2014-07-03 for curable composition and cured article.
This patent application is currently assigned to ADEKA CORPORATION. The applicant listed for this patent is Kenichiro Hiwatari, Kiyoshi Murata, Tomoaki Saiki, Atsuo Tomita. Invention is credited to Kenichiro Hiwatari, Kiyoshi Murata, Tomoaki Saiki, Atsuo Tomita.
Application Number | 20140187715 14/240804 |
Document ID | / |
Family ID | 47756189 |
Filed Date | 2014-07-03 |
United States Patent
Application |
20140187715 |
Kind Code |
A1 |
Hiwatari; Kenichiro ; et
al. |
July 3, 2014 |
CURABLE COMPOSITION AND CURED ARTICLE
Abstract
Provided are: a curable composition from which a cured article
having excellent molding processability and high heat resistance as
well as such a high Tg that it can be used as a molding resin for a
SiC power semiconductor can be obtained; and a cured article
thereof. The curable composition comprises: 100 parts by mass of a
compound having at least two partial structures represented by the
following Formula (1) in the molecule as a component (A); 0.5 to 3
parts by mass of a thermal radical generator as a component (B);
and 0 to 50 parts by mass of other radical-reactive compound as a
component (C): ##STR00001## (wherein, ring A represents a benzene
ring or a cyclohexyl ring; R.sup.1 represents an alkylene group
having 1 to 6 carbon atoms; R.sup.2 represents an alkyl group
having 1 to 4 carbon atoms; a represents a number of 0 or 1; b
represents an integer of 0 to 3; and c represents a number of 1 or
2).
Inventors: |
Hiwatari; Kenichiro; (Tokyo,
JP) ; Tomita; Atsuo; (Tokyo, JP) ; Saiki;
Tomoaki; (Tokyo, JP) ; Murata; Kiyoshi;
(Tokyo, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Hiwatari; Kenichiro
Tomita; Atsuo
Saiki; Tomoaki
Murata; Kiyoshi |
Tokyo
Tokyo
Tokyo
Tokyo |
|
JP
JP
JP
JP |
|
|
Assignee: |
ADEKA CORPORATION
Tokyo
JP
|
Family ID: |
47756189 |
Appl. No.: |
14/240804 |
Filed: |
August 24, 2012 |
PCT Filed: |
August 24, 2012 |
PCT NO: |
PCT/JP2012/071486 |
371 Date: |
February 25, 2014 |
Current U.S.
Class: |
524/852 ;
524/849; 526/286; 526/289; 526/313 |
Current CPC
Class: |
C08F 12/22 20130101;
C08F 228/04 20130101; H01L 2924/0002 20130101; C08F 112/34
20130101; C08K 7/18 20130101; H01L 2924/00 20130101; C09D 125/18
20130101; H01L 2924/0002 20130101; H01L 29/1608 20130101 |
Class at
Publication: |
524/852 ;
526/313; 526/289; 526/286; 524/849 |
International
Class: |
C08F 112/34 20060101
C08F112/34; C08K 7/18 20060101 C08K007/18; C08F 228/04 20060101
C08F228/04 |
Foreign Application Data
Date |
Code |
Application Number |
Aug 26, 2011 |
JP |
2011-185262 |
Claims
1. A curable composition, comprising: 100 parts by mass of a
compound having at least two partial structures represented by the
following Formula (1) in the molecule as a component (A); 0.5 to 3
parts by mass of a thermal radical generator as a component (B);
and 0 to 50 parts by mass of other radical-reactive compound as a
component (C): ##STR00020## (wherein, ring A represents a benzene
ring or a cyclohexyl ring; R.sup.1 represents an alkylene group
having 1 to 6 carbon atoms; R.sup.2 represents an alkyl group
having 1 to 4 carbon atoms; a represents a number of 0 or 1; b
represents an integer of 0 to 3; and c represents a number of 1 or
2).
2. The curable composition according to claim 1, wherein said
component (A) is a compound represented by the following Formula
(2) or (3): ##STR00021## (wherein, R.sup.3 represents an alkyl
group having 1 to 4 carbon atoms; d represents an integer of 0 to
2; X.sup.1 represents an oxygen atom, a sulfur atom, a sulfinyl
group, a sulfonyl group, a carbonyl group, a phenylene group, a
cyclohexylene group (however, 1,1-cyclohexylene group is excluded),
a group represented by the following Formula (4) or a direct bond;
and R.sup.1, R.sup.2, a, b and c have the same meanings as in said
Formula (1)) ##STR00022## (wherein, R.sup.4 and R.sup.5 each
independently represent a hydrogen atom, a trifluoromethyl group or
a hydrocarbon group having 1 to 12 carbon atoms, with a proviso
that, when R.sup.4 and R.sup.5 are hydrocarbon groups having 1 to
12 carbon atoms, R.sup.4 and R.sup.5 are optionally linked with
each other) ##STR00023## (wherein, R.sup.1, R.sup.2, a, b and c
have the same meanings as in said Formula (1)).
3. The curable composition according to claim 1, which further
comprises a filler as a component (D).
4. A tablet for transfer molding, which is composed of the curable
composition according to claim 1.
5. A cured article, which is obtained by curing the curable
composition according to claim 1.
6. A semiconductor element, which is obtained by molding a cured
article of the curable composition according to claim 1.
7. The curable composition according to claim 2, which further
comprises a filler as a component (D).
8. A tablet for transfer molding, which is composed of the curable
composition according to claim 2.
9. A tablet for transfer molding, which is composed of the curable
composition according to claim 3.
10. A cured article, which is obtained by curing the curable
composition according to claim 2.
11. A cured article, which is obtained by curing the curable
composition according to claim 3.
12. A semiconductor element, which is obtained by molding a cured
article of the curable composition according to claim 2.
13. A semiconductor element, which is obtained by molding a cured
article of the curable composition according to claim 3.
14. A tablet for transfer molding, which is composed of the curable
composition according to claim 7.
15. A cured article, which is obtained by curing the curable
composition according to claim 7.
16. A semiconductor element, which is obtained by molding a cured
article of the curable composition according to claim 7.
Description
TECHNICAL FIELD
[0001] The present invention relates to a curable composition and a
cured article thereof. More particularly, the present invention
relates to a curable composition from which a cured article having
excellent molding processability and high heat resistance can be
obtained, and a cured article thereof
BACKGROUND ART
[0002] SiC (silicon carbide) shows a lower electrical insulation
and a smaller energy loss at the time of electrification as
compared to silicon and thus has a smaller calorific value as well
as higher heat resistance. Therefore, as compared to silicon power
semiconductors, SiC power semiconductors are capable of handling a
larger electric power, so that SiC power semiconductors are being
actively studied as next-generation power semiconductors that would
replace silicon power semiconductors that are widely used at
present. The heat-resistance limit temperature of silicon power
semiconductor devices is about 150.degree. C.; however, in SiC
power semiconductor devices, the use thereof at a temperature of
240 to 300.degree. C. is being investigated so as to handle a
larger electric power, and heat resistance of higher than
240.degree. C. is demanded also for the members of SiC power
semiconductor devices.
[0003] Conventionally, as a molding resin of a semiconductor
obtained by molding a resin, an epoxy resin is mainly used. In
general, the physical properties of a resin, such as
viscoelasticity and thermal expansion coefficient, largely changes
across its Tg (glass transition temperature); therefore, it is
required that the Tg of a molding resin be higher than the service
temperature of the semiconductor. However, since the Tg of
conventional epoxy resins is about 200.degree. C. or lower, there
are problems of material softening, crack generation and the like
under such a service environment where the temperature exceeds
240.degree. C. (see, for example, Patent Documents 1 and 2). In
addition, since epoxy resins having a Tg of 240.degree. C. or
higher have high pre-curing melting points, their curing
temperatures are also high and curing requires a long time, so that
there are problems that other members are adversely affected and
the productivity is reduced (see, for example, Patent Document 3).
Furthermore, although the use of resins other than epoxy resins,
such as polyimide, has also been studied (see, for example, Patent
Document 4), such resins are not satisfactory in terms of required
performance.
[0004] Meanwhile, curable compositions containing a vinylbenzyl
ether compound of a polyvalent phenol compound are also known (see,
for example, Patent Documents 5 to 7); however, all of these
curable compositions have a Tg of lower than 240.degree. C. and are
thus not satisfactory as molding resins of SiC powder
semiconductors.
RELATED ART DOCUMENTS
Patent Documents
[0005] Patent Document 1: Japanese Unexamined Patent Application
Publication No. 2005-036085 [0006] Patent Document 2: Japanese
Unexamined Patent Application Publication No. 2006-269730 [0007]
Patent Document 3: Japanese Unexamined Patent Application
Publication No. 2011-184650 [0008] Patent Document 4: Japanese
Unexamined Patent Application Publication No. 2010-222392 [0009]
Patent Document 5: Japanese Unexamined Patent Application
Publication No. 2000-258932 [0010] Patent Document 6: Japanese
Unexamined Patent Application Publication No. 2004-189901 [0011]
Patent Document 7: Japanese Unexamined Patent Application
Publication No. 2010-202778
SUMMARY OF THE INVENTION
Problems to be Solved by the Invention
[0012] Therefore, an object of the present invention is to provide
a curable composition from which a cured article having excellent
molding processability and high heat resistance as well as such a
high Tg that it can be used as a molding resin for a SiC power
semiconductor can be obtained; and a cured article thereof
Means for Solving the Problems
[0013] In view of the above-described problems, the present
inventors intensively studied to discover that a curable
composition comprising a compound having a specific structure has
excellent molding processability and high post-curing heat
resistance, thereby completing the present invention. That is, the
present invention provides a curable composition which comprises:
100 parts by mass of a compound having at least two partial
structures represented by the following Formula (1) in the molecule
as a component (A); 0.5 to 3 parts by mass of a thermal radical
generator as a component (B); and 0 to 50 parts by mass of other
radical-reactive compound as a component (C):
##STR00002##
[0014] (wherein, ring A represents a benzene ring or a cyclohexyl
ring; R.sup.1 represents an alkylene group having 1 to 6 carbon
atoms; R.sup.2 represents an alkyl group having 1 to 4 carbon
atoms; a represents a number of 0 or 1; b represents an integer of
0 to 3; and c represents a number of 1 or 2).
[0015] In the curable composition according to the present
invention, it is preferred that the above-described component (A)
be a compound represented by the following Formula (2) or (3):
##STR00003##
[0016] (wherein, R.sup.3 represents an alkyl group having 1 to 4
carbon atoms; d represents an integer of 0 to 2; X.sup.1 represents
an oxygen atom, a sulfur atom, a sulfinyl group, a sulfonyl group,
a carbonyl group, a phenylene group, a cyclohexylene group
(however, 1,1-cyclohexylene group is excluded), a group represented
by the following Formula (4) or a direct bond; and R.sup.1,
R.sup.2, a, b and c have the same meanings as in the Formula
(1))
##STR00004##
[0017] (wherein, R.sup.4 and R.sup.5 each independently represent a
hydrogen atom, a trifluoromethyl group or a hydrocarbon group
having 1 to 12 carbon atoms, with a proviso that, when R.sup.4 and
R.sup.5 are hydrocarbon groups having 1 to 12 carbon atoms, R.sup.4
and R.sup.5 are optionally linked with each other)
##STR00005##
[0018] (wherein, R', R.sup.2, a, b and c have the same meanings as
in the Formula (1)).
[0019] It is also preferred that the curable composition according
to the present invention further comprise a filler as a component
(D).
[0020] The tablet for transfer molding according to the present
invention is composed of the above-described curable
composition.
[0021] The cured article according to the present invention is
obtained by curing the above-described curable composition.
[0022] The semiconductor element according to the present invention
is obtained by molding a cured article of the above-described
curable composition.
Effects of the Invention
[0023] According to the present invention, a curable composition
from which a cured article having excellent molding processability
and high heat resistance can be obtained and a cured article
thereof can be provided. The curable composition of the present
invention is useful particularly as a molding material for
semiconductors and the like.
MODE FOR CARRYING OUT THE INVENTION
[0024] The curable composition of the present invention is a
curable composition which comprises: a compound having at least two
partial structures represented by the above-described Formula (1)
in the molecule as a component (A); a radical generator as a
component (B); and, optionally, other radical-reactive compound as
a component (C).
[0025] First, the component (A) will be described. In the
above-described Formula (1), R' represents an alkylene group having
1 to 6 carbon atoms. Examples of the alkylene group having 1 to 6
carbon atoms include a methylene group, an ethylene group, a
propylene group, a butylene group, a pentylene group, a hexylene
group, a 1-methylethylene group, a 2-methylethylene group, a
2-methylpropylene group and a 2,2-dimethylpropylene group. From the
standpoint of the ease of production, R.sup.1 is preferably a
methylene group. R.sup.2 represents an alkyl group having 1 to 4
carbon atoms and b represents an integer of 0 to 3. From the
standpoint of the material availability, b is preferably 0.
Examples of the alkyl group having 1 to 4 carbon atoms include a
methyl group, an ethyl group, a propyl group, an isopropyl group, a
butyl group, a 1-methylpropyl group, an isobutyl group and a
t-butyl group.
[0026] In the above-described Formula (1), a represents a number of
0 or 1 and c represents a number of 1 or 2. From the standpoint of
the ease of production, a is preferably 1. Further, c is preferably
1 because good storage stability is attained and an abnormal
reaction is not likely to occur during a curing reaction of the
curable composition of the present invention.
[0027] In the above-described Formula (1), the ring A represents a
benzene ring or a cyclohexyl ring and, from the standpoint of
improving the heat resistance, the ring A is preferably a benzene
ring. The component (A) of the present invention is a compound
having at least two partial structures represented by the
above-described Formula (1) in the molecule, in which the ring A or
a part thereof is optionally overlapping. From the standpoint of
reducing the thermal expansion coefficient of the resulting cured
article, it is preferred that the component (A) of the present
invention be a compound having two partial structures represented
by the above-described Formula (1) in the molecule.
[0028] The compound having at least two partial structures
represented by the above-described Formula (1) in the molecule can
be rephrased as "a compound having at least two partial structures
represented by the following Formula (1a) in the molecule, in which
the hydrogen atom of the hydroxyl group is substituted with a group
represented by the Formula (1b)":
##STR00006##
[0029] (wherein, ring A has the same meaning as in the Formula
(1))
##STR00007##
[0030] (wherein, R.sup.1, R.sup.2, a, b and c have the same
meanings as in the Formula (1)).
[0031] Among compounds having at least two partial structures
represented by the above-described Formula (1a) in the molecule,
from the standpoint of reducing the thermal expansion coefficient
of the resulting cured article, those compounds that are
represented by the following Formula (2a) or (3a) are more
preferred:
##STR00008##
[0032] (wherein, R.sup.3 represents an alkyl group having 1 to 4
carbon atoms; d represents an integer of 0 to 2; X.sup.1 represents
an oxygen atom, a sulfur atom, a sulfinyl group, a sulfonyl group,
a carbonyl group, a phenylene group, a cyclohexylene group
(however, 1,1-cyclohexylene group is excluded), a group represented
by the following Formula (4) or a direct bond)
##STR00009##
[0033] (wherein, R.sup.4 and R.sup.5 each independently represent a
hydrogen atom, a trifluoromethyl group or a hydrocarbon group
having 1 to 12 carbon atoms, with a proviso that, when R.sup.4 and
R.sup.5 are hydrocarbon groups having 1 to 12 carbon atoms, R.sup.4
and R.sup.5 are optionally linked with each other).
##STR00010##
[0034] In the above-described Formula (2a), R.sup.3 represents an
alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group
having 1 to 4 carbon atoms include the same groups as those
exemplified for R.sup.2 of the above-described Formula (1) and,
from the standpoint of attaining good heat resistance, R.sup.3 is
preferably a methyl group or a t-butyl group. Further, d represents
an integer of 0 to 2 and, from the standpoint of reducing the
thermal expansion coefficient of a cured article obtained from the
curable composition of the present invention, d is preferably 0.
X.sup.1 represents an oxygen atom, a sulfur atom, a sulfonyl group,
a sulfonyl group, a carbonyl group, a phenylene group, a
cyclohexylene group (however, 1,1-cyclohexylene group is excluded),
a group represented by the above-described Formula (4) or a direct
bond. From the standpoint of reducing the thermal expansion
coefficient of a cured article obtained from the curable
composition of the present invention, it is preferred that the
hydroxyl groups of the above-described Formula (2a) be each bound
at para-position to X.sup.1.
[0035] Examples of the phenylene group include a 1,2-phenylene
group, a 1,3-phenylene group and a 1,4-phenylene group. Examples of
the cyclohexylene group (however, 1,1-cyclohexylene group is
excluded) include 1,2-cyclohexylene group, 1,3-cyclohexylene group
and 1,4-cyclohexylene group.
[0036] In the above-described Formula (4), R.sup.4 and R.sup.5 each
independently represent a hydrogen atom, a trifluoromethyl group or
a hydrocarbon group having 1 to 12 carbon atoms. However, when
R.sup.4 and R.sup.5 are hydrocarbon groups having 1 to 12 carbon
atoms, R.sup.4 and R.sup.5 are optionally linked with each other.
Examples of the group represented by the Formula (4) include the
following groups:
##STR00011##
[0037] Among those compounds represented by the above-described
Formula (2a), examples of a compound in which X.sup.1 is an oxygen
atom include bis(2-hydroxyphenyl)ether and
bis(4-hydroxyphenyl)ether.
[0038] Among those compounds represented by the above-described
Formula (2a), examples of a compound in which X.sup.1 is a sulfur
atom, a sulfinyl group or a sulfonyl group include
2,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfide
(also referred to as "bisphenol T"), 4,4'-dihydroxydiphenyl
sulfoxide, 2,2'-dihydroxydiphenyl sulfone, 2,4'-dihydroxydiphenyl
sulfone and 4,4'-dihydroxydiphenyl sulfone (also referred to as
"bisphenol S").
[0039] Among those compounds represented by the above-described
Formula (2a), examples of a compound in which X.sup.1 is a carbonyl
group include 2,4'-dihydroxybenzophenone and
4,4'-dihydroxybenzophenone.
[0040] Among those compounds represented by the above-described
Formula (2a), examples of a compound in which X.sup.1 is a
phenylene group include 4,4'-(1,2-phenylene)bisphenol,
4,4'-(1,3-phenylene)bisphenol and
4,4'-(1,4-phenylene)bisphenol.
[0041] Among those compounds represented by the above-described
Formula (2a), examples of a compound in which X' is a cyclohexylene
group (however, 1,1-cyclohexylene group is excluded) include
4,4'-(1,2-cyclohexylene)bisphenol,
4,4'-(1,3-cyclohexylene)bisphenol and
4,4'-(1,4-cyclohexylene)bisphenol.
[0042] Among those compounds represented by the above-described
Formula (2a), examples of a compound in which X.sup.1 is a direct
bond include biphenyl-2,2'-diol, biphenyl-2,4'-diol and
biphenyl-4,4'-diol.
[0043] Among those compounds represented by the above-described
Formula (2a), examples of a compound in which X.sup.1 is a group
represented by the above-described Formula (4) include
2,2'-methylenebisphenol, 2,4'-methylenebisphenol,
4,4'-methylenebisphenol, 2,2'-ethylenebisphenol,
2,4'-ethylenebisphenol, 4,4'-ethylenebisphenol,
4,4'-ethylidenebisphenol, 2,4'-isopropylidenebisphenol,
4,4'-isopropylidenebisphcnol (also referred to as "bisphenol A"),
4,4'-butylidenebisphenol, 4,4'-isobutylidenebisphenol,
4,4'-sec-butylidenebisphenol (also referred to as "bisphenol B"),
4,4'-isopropylidenebis(2-methylphenol) (also referred to as
"bisphenol C"), 4,4'-(1,3-dimethylbutylidene)bisphenol (also
referred to as "Bis MIBK"), 4,4'-hexylidenebisphenol,
4,4'-(1-methylpentylidene)bisphenol,
4,4'-(1-methylhexylidene)bisphenol, 4,4'-heptylidenebisphenol,
4,4'-isopropylidenebis(2,6-dimethylphenol) (also referred to as
"bisxylenol A"), 4,4'42-ethylhexylidene)bisphenol,
4,4'-octylidenebisphenol, 4,4'-(1-methyloctylidene)bisphenol,
4,4'-isopropylidenebis(3-t-butylphenol),
4,4'-(1-phenylethylidene)bisphenol,
4,4'-(1-phenylethylidene)bisphenol (also referred to as "bisphenol
AP"), 4,4'-(1-phenylethylidene)bis(3-t-butylphenol),
4,4'-(1-benzylethylidene)bisphenol,
4,4'-(1-(4-methyl)phenylethylidene)bis(3-t-butylphenol),
4,4'-(1-(4-phenyl)phenylethylidene)bis(3-t-butylphenol),
4,4'-dihydroxytetraphenyl methane, 4,4'-cyclohexylidene diphenol,
4,4'-(3,3,5-trimethylcyclohexylidene)diphenol,
4,4'-(2-norbornylidene)diphenol,
4,4'-(octahydro-4,7-methano-5H-indene-5-ylidene)bisphenol,
4,4'-(indan-1-ylidene)diphenol,
4,4'-(3-phenylindan-1-ylidene)diphenol,
4,4'-(fluorene-9-ylidene)diphenol and
6,6'-dihydroxy-3,3,3',3'-tetramethyl-1,1'-spirobiindan.
[0044] Since a cured article having a high glass transition
temperature can be obtained, among those compounds represented by
the above-described Formula (2a), ones in which X.sup.1 is a sulfur
atom, a sulfonyl group, a phenylene group, a group represented by
the Formula (4) or a direct bond are preferred and, among those
groups represented by the Formula (4), ones in which at least
either of R.sup.4 and R.sup.5 is a hydrocarbon group having a
benzene ring are preferred.
[0045] Examples of a compound represented by the Formula (3a)
include naphthalene-1,2-diol, naphthalene-1,3-diol,
naphthalene-1,4-diol, naphthalene-1,5-diol, naphthalene-1,6-diol,
naphthalene-1,8-diol, naphthalene-2,3-diol, naphthalene-2,6-diol
and naphthalene-2,7-diol. It is noted here that the compound
represented by the Formula (3a) is a compound in which a part of
the ring A is overlapping.
[0046] Since a cured article having a high glass transition
temperature can be obtained, among those compounds represented by
the above-described Formula (2a) or (3a), compounds represented by
the Formula (2a) in which X.sup.1 is a sulfur atom, a sulfonyl
group, a phenylene group, a group represented by the Formula (4) or
a direct bond or compounds represented by the Formula (3a) are
preferred, and compounds represented by the Formula (2a) in which
X' is a group represented by the Formula (4) are more preferred.
Among such compounds represented by the Formula (2a) in which
X.sup.1 is a group represented by the Formula (4), ones in which at
least either of R.sup.4 and R.sup.5 is a hydrocarbon group having a
benzene ring are preferred, and ones in which either R.sup.4 or
R.sup.5 is a phenyl group and the other is a methyl group are more
preferred.
[0047] Among those compounds having at least two partial structures
represented by the above-described Formula (1a) in the molecule,
examples of a compound that is not a compound represented by the
above-described Formula (2a) or (3a) include cyclohexane
ring-containing diol compounds such as 1,2-cyclohexanediol,
1,3-cyclohexanediol, 1,4-cyclohexanediol, 4,4'-dicyclohexanediol,
2,2'-isopropylidene dicyclohexanol, 4,4'-isopropylidene
dicyclohexanol (also referred to as "hydrogenated bisphenol A"),
bicyclo[2,2,1]heptane-2,3-diol, bicyclo[2,2,1]heptane-2,5-diol,
bicyclo[2,2,1]heptane-2,7-diol,
octahydro-4,7-methano-1H-indene-5,6-diol, adamantane-1,3-diol,
1,2,3,4-tetrahydronaphthalene-1,5-diol,
1,2,3,4-tetrahydronaphthalene-5,8-diol and 1,5-decalindiol;
[0048] benzenediol compounds such as 1,2-benzenediol,
1,3-benzenediol, 1,4-benzenediol and 2-methyl-1,3-benzenediol;
[0049] diphenol compounds such as
4,4'-(1,1,3-trimethyltrimethylene)bisphenol,
3,4-bis(4-hydroxyphenyl)hexane, 1,3-bis(4-hydroxycumyl)benzene
(also referred to as "bisphenol M"), 1,4-bis(4-hydroxycumyl)benzene
(also referred to as "bisphenol P"),
4,4'-(phenylphosphinylidene)bisphenol,
4,4'-(tetrafluoroisopropylidene)bisphenol (also referred to as
"bisphenol AF"), 4,4'-isopropylidenebis(3,5-dibromophenol) (also
referred to as "tetrabromobisphenol A"), reaction product between
dicyclopentadiene and phenol, and
4,4'-oxybis(ethylenethio)diphenol;
[0050] triphenol compounds such as tris(4-hydroxyphenyl)methane
(also referred to as "trisphenol PHBA"),
1,1,3-tris(4-hydroxyphenyl)propane (also referred to as "trisphenol
PA"),
4,4'-[1-{4-(4-hydroxyphenylisopropylidene)phenyl}ethylidene]bisphenol,
2,4,6-tris(4-hydroxyphenoxy)-1,3,5-triazine and
2,4,6-tris(4-hydroxyphenyl)amino-s-triazine;
[0051] tetraphenol compounds such as
1,1,2,2-tetrakis(4-hydroxyphenyl)ethane,
1,4-bis[bis(4-hydroxyphenyl)methyl]benzene,
1,4-bis[.alpha.,.alpha.-bis(4-hydroxyphenyl)benzyl]benzene,
bis[4,4-bis(4-hydroxyphenyl)cyclohexane] and
isopropylidene-bis[4,4-bis(4-hydroxyphenyl)cyclohexane];
[0052] naphthol compounds such as 1,1'-binaphthalene-2,2'-diol,
2,2'-binaphthalene-1,1'-diol and 1,1'-thiobis-2-naphthol; phenol
novolac compounds; cresol novolac compounds; and hydroxystyrene
oligomers.
[0053] Among these compounds, cyclohexane diol compounds and
benzene diol compounds are compounds in which the ring A is
overlapping, and 1,2,3,4-tetrahydronaphthalene-1,5-diol,
1,5-decalin diol and the like are compounds in which the ring A is
partially overlapping.
[0054] When the compound having two partial structures represented
by the Formula (1a) in the molecule is a compound represented by
the above-described Formula (2a) or (3a), the component (A) of the
curable composition of the present invention is a compound
represented by the following Formula (2) or (3):
##STR00012##
[0055] (wherein, R.sup.1, R.sup.2, a, b and c have the same
meanings as in the Formula (1); and R.sup.3, d and X.sup.1 have the
same meanings as in the Formula (2a))
##STR00013##
[0056] (wherein, R.sup.1, R.sup.2, a, b and c have the same
meanings as in the Formula (1)).
[0057] Next, a method of synthesizing the component (A) of the
present invention will be described. The method of synthesizing the
component (A) is not particularly restricted and, for example, in
cases where a in the above-described Formula (1) is 1, the
component (A) may be synthesized by allowing a compound having at
least two partial structures represented by the above-described
Formula (1a) in the molecule and a halogen compound represented by
the following Formula (1c) to undergo an etherification reaction in
accordance with the Williamson method, which is a commonly used
ether synthesis method:
##STR00014##
[0058] (wherein, X.sup.2 represents a halogen atom; and R.sup.1,
R.sup.2, b and c have the same meanings as in the Formula (1)).
[0059] In the Formula (1c), X.sup.2 represents a halogen atom, and
R.sup.1, R.sup.2, b and c have the same meanings as in the Formula
(1). Examples of the halogen atom include a chlorine atom, a
bromine atom and an iodine atom and, from the standpoints of good
reactivity and material availability, X.sup.2 is preferably a
chlorine atom or a bromine atom, more preferably a chlorine
atom.
[0060] Next, the component (B) of the present invention, which is a
thermal radical generator, will be described. In the present
invention, the term "thermal radical generator" refers to a
compound which generates a radical by the action of heat, and
examples thereof include organic peroxide-based thermal radical
generators and azo compound-based thermal radical generators.
[0061] Examples of the organic peroxide-based thermal radical
generators include diisobutyryl peroxide, cumylperoxy neodecanoate,
3-hydroxy-1,1-dimethylbutylperoxy neodecanoate, dipropylperoxy
dicarbonate, diisopropylperoxy dicarbonate, di-sec-butylperoxy
dicarbonate, 1,1,3,3-tetramethylbutylperoxy neodecanoate,
bis(4-t-butylcyclohexyl)peroxy dicarbonate, bis(2-ethylhexyl)peroxy
dicarbonate, t-hexylperoxy neodecanoate, t-butylperoxy
neodecanoate, t-butylperoxy neoheptanoate, t-heptylperoxy pivalate,
t-butylperoxy pivalate, t-pentylperoxy pivalate,
bis(3,5,5-trimethylhexanoyl)peroxide, dilauroyl peroxide,
1,1,3,3-tetramethylbutylperoxy-2-ethyl hexanoate, disuccinic acid
peroxide, 1,1,3,3-tetramethylbutylperoxy-2-ethyl hexanoate,
t-pentylperoxy-2-ethyl hexanoate, t-butylperoxy-2-ethyl hexanoate,
1,1-di(t-hexylperoxy)cyclohexane, 1,1-di(t-butylperoxy)cyclohexane,
1,1-di(t-pentylperoxy)cyclohexane,
2,2-bis(4,4-di(t-butylperoxy)cyclohexyl propane,
t-hexylperoxyisopropyl monocarbonate, t-pentylperoxyisopropyl
carbonate, t-pentylperoxy-n-octoate, t-butylperoxy maleate,
1,1-di(t-butylperoxy)cyclohexane, t-butylperoxy-3,5,5-trimethyl
hexanoate, t-butylperoxy laurate, t-butylperoxyisopropyl
monohexanoate, t-pentylperoxy-2-ethylhexyl carbonate,
t-butylperoxy-2-ethylhexyl monohexanoate, t-hexylperoxy benzoate,
t-pentylperoxy acetate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane,
t-butylperoxy acetate, 2,2-di(t-butylperoxy)butane, t-butylperoxy
benzoate, butyl-4,4-di(t-butylperoxy)valerate,
ethyl-3,3-di(t-butylperoxy)butyrate,
bis(2-t-butylperoxyisopropyl)benzene, dicumyl peroxide, di-t-hexyl
peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, di-t-butyl
peroxide, t-butylperoxy isobutyrate and
2,5-dimethyl-2,5-di(t-butylperoxy)hexane.
[0062] Examples of the azo compound-based thermal radical
generators include
2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile),
2,2'-azobis(2,4-dimethylvaleronitrile),
2,2'-azobis(2-methylbutyronitrile),
1,1'-azobis(cyclohexyl-1-carbonitrile),
2,2'-azobis(N-(2-propyl)-2-methylpropionamide),
1-((1-cyano-1-methylethyl)azo)formamide,
2,2'-azobis(N-butyl-2-methylpropionamide),
2,2'-azobis(N-cyclohexyl-2-methylpropionamide) and
2,2'-azobis-isobutyronitrile.
[0063] From the standpoints of allowing the curable composition to
have good storage stability and obtaining a cured article having a
high Tg, it is preferred that the component (B) of the present
invention be an organic peroxide-based thermal radical generator.
The organic peroxide-based thermal radical generator may be
appropriately selected in accordance with the processing
temperature of the curable composition of the present invention
and, for example, in cases where the curable composition of the
present invention is molded by transfer molding, the organic
peroxide-based thermal radical generator has a 1-minute half-life
temperature of preferably 140 to 200.degree. C., more preferably
150 to 180.degree. C.
[0064] In the curable composition of the present invention, the
amount of the component (B) to be blended is 0.5 to 3 parts by mass
with respect to 100 parts by mass of the component (A). When the
amount of the component (B) is less than 0.5 parts by mass, a cured
article having a high Tg may not be obtained, while when the amount
is greater than 3 parts by mass, the physical properties of the
resulting cured article, such as hardness and elasticity, may be
adversely affected. The amount of the component (B) to be blended
is preferably 0.6 to 2.5 parts by mass, more preferably 0.7 to 2
parts by mass, most preferably 0.8 to 1.5 parts by mass, with
respect to 100 parts by mass of the component (A).
[0065] Many of the compounds of the component (A) of the present
invention have a high melting point, so that there may be a problem
in terms of the workability of the curable composition of the
present invention. Therefore, in the curable composition of the
present invention, in order to lower its softening point, as a
component (C), other radical-reactive compound may also be
incorporated in an amount of 0 to 50 parts by mass with respect to
100 parts by mass of the component (A). In the present invention,
the term "other radical-reactive compound" refers to a compound
which has radical reactivity and is different from the compound of
the component (A) that has at least two partial structures
represented by the above-described Formula (1) in the molecule. As
such other radical-reactive compound, a compound having at least
two radical-reactive groups, preferably ethylenically unsaturated
bonds, in the molecule is preferred since such a compound causes
only a small reduction in the mechanical and physical properties of
the cured article of the present invention.
[0066] Examples of compounds that are preferred as the component
(C) include divinylbenzene, trivinylbenzene, 2,3-divinyl
naphthalene, 2,3-divinylpyridine, diallyl phthalate, triallyl
trimellitate, tetraallyl pyromellitate, diallyl
tetrahydrophthalate, diallyl hexahydrophthalate,
2,3-divinyl-2-cyclohexene-1-ol, diethylene glycol bis(allyl
carbonate), trimethylolpropane diallyl ether, trimethylolpropane
trimethacrylate, trimethylolpropane triacrylate,
1,1,2,2-tetraallyloxy ethane, diallylidene pentaerythritol,
triallyl cyanurate, triallyl isocyanurate, glycidyldiallyl
isocyanurate, diallyl ether of 2,2-bis(4-hydroxycyclohexyl)propane,
1,4-divinylcyclohexane, 1,2,4-trivinylcyclohexane, divinylbiphenyl,
1,3-diisopropenyl benzene, 1,4-diisopropenyl benzene, 3,3'-diallyl
bisphenol A, 3,5,3',5'-tetraallyl bisphenol A,
1,2-bis(dimethylvinylsilyl)benzene,
1,3-bis(dimethylvinylsilyl)benzene,
1,4-bis(dimethylvinylsilyl)benzene, 1,1,3,3-tetraphenyl-1,3-divinyl
disiloxane and 1,1,5,5-tetramethyl-3,3-diphenyl-1,5-divinyl
trisiloxane. Thereamong, from the standpoint of allowing the
curable composition of the present invention to have good storage
stability and because of good reactivity with the component (A),
diallyl phthalate, triallyl trimellitate, tetraallyl pyromellitate,
diallyl tetrahydrophthalate, diallyl hexahydrophthalate, triallyl
cyanurate, triallyl isocyanurate, glycidyldiallyl isocyanurate,
1,4-divinylcyclohexane, 1,2,4-trivinylcyclohexane, 3,3'-diallyl
bisphenol A, 3,3',5,5'-tetraallyl bisphenol A,
1,2-bis(dimethylvinylsilyl)benzene,
1,3-bis(dimethylvinylsilyl)benzene,
1,4-bis(dimethylvinylsilyl)benzene, 1,1,3,3-tetraphenyl-1,3-divinyl
disiloxane and 1,1,5,5-tetramethyl-3,3-diphenyl-1,5-divinyl
trisiloxane triallyl isocyanurate are preferred; diallyl phthalate,
triallyl cyanurate, triallyl isocyanurate, 3,3'-diallyl bisphenol
A, 3,3',5,5'-tetraallyl bisphenol A,
1,4-bis(dimethylvinylsilyl)benzene, 1,1,3,3-tetraphenyl-1,3-divinyl
disiloxane and 1,1,5,5-tetramethyl-3,3-diphenyl-1,5-divinyl
trisiloxane are more preferred; and triallyl isocyanurate is most
preferred.
[0067] The component (C) may be blended in such an amount that the
curable composition of the present invention has a softening point
at which molding thereof is easily carried out as long as the
amount is 50 parts by mass or less with respect to 100 parts by
mass of the component (A). When the amount of the component (C) is
excessively large, the physical properties of the resulting cured
article of the curable composition of the present invention may be
deteriorated. Therefore, the amount of the component (C) is
preferably 0 to 30 parts by mass, more preferably 0 to 20 parts by
mass, with respect to 100 parts by mass of the component (A).
[0068] It is preferred that the curable composition of the present
invention further comprise a filler as a component (D) since it can
improve the mechanical strength, heat resistance and the like of
the resulting cured article and reduce the thermal expansion
coefficient. Examples of the filler include silica-based inorganic
fillers such as quartz, fumed silica, precipitated silica, silicic
acid anhydride, molten silica, crystalline silica and ultrafine
powder amorphous silica; inorganic layered substances such as
magadiite, montmorillonite, saponite, kaolinite, ilerite and mica;
fibrous fillers such as aramid fibers, silicon carbide fibers,
ceramic fibers, asbestos fibers, gypsum fibers, metal fibers, glass
fibers, alumina fibers and carbon fibers; nitride-based inorganic
fillers such as silicon nitride, boron nitride and aluminum
nitride; metal oxide-based inorganic fillers such as titanium
oxide, zinc oxide, zirconium oxide, niobium oxide, aluminum oxide,
cerium oxide and yttrium oxide; carbon-based inorganic fillers such
as silicon carbide, black lead, diamond, carbon blacks and
graphites; metal powders such as copper powder, aluminum powder,
nickel powder and silver powder; carbonates such as calcium
carbonate, magnesium carbonate and dolomite; silicates such as
alumina silicate and magnesium silicate; sulfates such as calcium
sulfate and barium sulfate; potassium titanate; barium titanate;
aluminum borate; aluminum hydroxide; diatomaceous earth; white
earth; clay; talc; wollastonite; zeolite; sericite; kaolin;
pyrophyllite; bentonite; asbestos; glass beads; glass flakes; and
ceramic beads. Thereamong, from the standpoint of obtaining a cured
article having a low thermal expansion coefficient, silica-based
inorganic fillers, aluminum oxide and aluminum nitride are
preferred; silica-based inorganic fillers are more preferred; and
molten silica is most preferred. The shape of the filler is
preferably spherical and the particle size is preferably in the
range of 10 to 50 .mu.m since such a filler allows the curable
composition of the present invention to have good fluidity.
[0069] When the amount of the component (D) contained in the
curable composition of the present invention is excessively large,
there may be adverse effects on the strength, bending elasticity
and the like of the cured article of the present invention;
therefore, the amount of the component (D) to be contained is
preferably 10 to 85 parts by mass, more preferably 20 to 80 parts
by mass, with respect to 100 parts by mass of the curable
composition of the present invention.
[0070] In the curable composition of the present invention, in
addition to the components (A) to (D), an additive(s) imparting
weather resistance, physical stability, mold-releasing property,
storage stability and the like can be used as well. Examples of
such additives include antioxidants, ultraviolet absorbers,
hindered amine-based light stabilizers, flame retardants, silane
coupling agents and mold-releasing agents. In cases where such
additive(s) is/are blended, the amount thereof can be appropriately
selected in accordance with the intended purpose and the like of
each additive; however, from the standpoint of not adversely
affecting the effects of the present invention, the total amount of
all additives is preferably in the range of 10 parts by mass or
less with respect to 100 parts by mass of the curable composition
of the present invention.
[0071] An antioxidant is an additive which inhibits oxidation and
imparts heat resistance and weather resistance, and examples
thereof include phenol-based antioxidants, phosphorus-based
antioxidants and thioether-based antioxidants. Examples of the
phenol-based antioxidants include 2,6-di-t-butylphenol,
2,6-di-t-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxy phenol,
distearyl(3,5-di-t-4-hydroxybenzyl)phosphonate,
1,6-hexamethylenebis[(3,5-di-t-4-hydroxyphenyl)propionic acid
amide], 4,4'-thiobis(6-t-butyl-m-cresol),
2,2'-methylenebis(4-methyl-6-t-butylphenol),
2,2'-methylenebis(4-ethyl-6-t-butylphenol),
4,4'-butylidenebis(6-t-butyl-m-cresol),
2,2'-ethylidenebis(4,6-di-t-butylphenol),
2,2'-ethylidenebis(4-sec-butyl-6-t-butylphenol),
1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane,
1,3,5-tris(2,6-dimethyl-3-hydroxy-4-t-butylbenzyl)isocyanurate,
1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate,
1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,
2-t-butyl-4-methyl-6-(2-acryloyloxy-3-t-butyl-5-methylbenzyl)phenol,
stearyl(3,5-di-t-butyl-4-hydroxyphenyl)propionate, thiodiethylene
glycol-bis[(3,5-di-t-butyl-4-hydroxyphenyl)propionate],
1,6-hexamethylenebis[(3,5-di-t-butyl-4-hydroxyphenyl)propionate],
bis[3,3-bis(4-hydroxy-3-t-butylphenyl)butyric acid]glycol ester,
bis[2-t-butyl-4-methyl-6-(2-hydroxy-3-t-butyl-5-methylbenzyl)phenyl]terep-
hthalate,
1,3,5-tris[(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxyethyl]iso-
cyanurate,
3,9-bis[1,1-dimethyl-2-{(3-t-butyl-4-hydroxy-5-methylphenyl)pro-
pionyloxy}ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane and
triethylene
glycol-bis[(3-t-butyl-4-hydroxy-5-methylphenyl)propionate].
[0072] Examples of the phosphorus-based antioxidants include
[2-t-butyl-4-(3-t-butyl-4-hydroxy-5-methylphenylthio)-5-methylphenyl]phos-
phite, tridecyl phosphite, octyldiphenyl phosphite,
di(decyl)monophenyl phosphite, di(tridecyl)pentaerythritol
diphosphite, di(nonylphenyl)pentaerythritol diphosphite,
bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite,
bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite,
bis(2,4,6-tri-t-butylphenyl)pentaerythritol diphosphite,
bis(2,4-dicumylphenyl)pentaerythritol di phosphite,
tetra(tridecyl)isopropylidene diphenol diphosphite,
tetra(tridecyl)-4,4'-n-butylidenebis(2-t-butyl-5-methylphenol)diphosphite-
,
hexa(tridecyl)-1,1,3-tris(2-methyl-4-hydroxy-5t-butylphenyl)butane
triphosphite, tetrakis(2,4-di-t-butylphenyl)biphenylene
diphosphonite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide,
2,2'-methylenebis(4,6-t-butylphenyl)-2-ethylhexyl phosphite,
2,2'-methylenebis(4,6-t-butylphenyl)-octadecyl phosphite,
2,2'-ethylidenebis(4,6-di-t-butylphenyl)fluorophosphite,
2-ethyl-2-butyl propylene glycol and 2,4,6-tri-t-butyl phenol.
[0073] Examples of the thioether-based antioxidants include dialkyl
thiodipropionates such as dilauryl thiodipropionate, dimyristyl
thiodipropionate and distearyl thiodipropionate; and
.beta.-alkylmercaptopropionic acid esters of polyols, such as
pentaerythritol tetra(.beta.-dodecylmercaptopropionate).
[0074] The amount of the antioxidant(s) to be blended is preferably
0.001 to 10 parts by mass, more preferably 0.05 to 5 parts by mass,
with respect to 100 parts by mass of the curable composition of the
present invention. It is noted here that the phenol-based
antioxidants also have an effect of improving the storage stability
of the curable composition of the present invention.
[0075] An ultraviolet absorber is an additive which absorbs
ultraviolet radiation and imparts weather resistance, and examples
thereof include benzotriazole-based ultraviolet absorbers,
triazine-based ultraviolet absorbers and benzophenone-based
ultraviolet absorber.
[0076] Examples of the benzotriazole-based ultraviolet absorbers
include 2-(2'-hydroxy-5'-methylphenyl)benzotriazole,
2-(2'-hydroxy-3',5'-di-t-butylphenyl)-5-chlorobenzotriazole,
2-(2'-hydroxy-3'-t-butyl-5'-methylphenyl)-5-chlorobenzotriazole,
2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole,
2-(2'-hydroxy-3',5'-dicumylphenyl)benzotriazole,
2-(2'-hydroxy-3'-t-butyl-5'-carboxyphenyl)benzotriazole and
2,2'-methylenebis(4-t-octyl-6-benzotriazolyl)phenol.
[0077] Examples of the triazine-based ultraviolet absorbers include
2-(2-hydroxy-4-octoxyphenyl)-4,6-bis(2,4-dimethylphenyl)-s-triazine,
2-(2-hydroxy-4-hexyloxyphenyl)-4,6-diphenyl-s-triazine,
2-(2-hydroxy-4-propoxy-5-methylphenyl)-4,6-bis(2,4-dimethylphenyl)-s-tria-
zine, 2-(2-hydroxy-4-hexyloxyphenyl)-4,6-dibiphenyl-s-triazine,
2,4-bis(2-hydroxy-4-octoxyphenyl)-6-(2,4-dimethylphenyl)-s-triazine
and 2,4,6-tris(2-hydroxy-4-octoxyphenyl)-s-triazine.
[0078] Examples of the benzophenone-based ultraviolet absorbers
include 2,4-dihydroxy benzophenone, 2-hydroxy-4-methoxy
benzophenone, 2-hydroxy-4-octoxy benzophenone and
5,5'-methylenebis(2-hydroxy-4-methoxybenzophenone).
[0079] The amount of the above-described ultraviolet absorber(s) to
be blended is preferably 0.01 to 10 parts by mass, more preferably
0.05 to 5 parts by mass, with respect to 100 parts by mass of the
curable composition of the present invention.
[0080] A hindered amine-based light stabilizer is an additive which
traps radicals generated by ultraviolet radiation and the like and
imparts weather resistance, and examples thereof include
2,2,6,6-tetramethyl-4-piperidyl stearate,
1,2,2,6,6-pentamethyl-4-piperidyl stearate,
2,2,6,6-tetramethyl-4-piperidyl benzoate,
bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate,
bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate,
bis(1-octoxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate,
1,2,2,6,6-pentamethyl-4-piperidyl methacrylate,
2,2,6,6-tetramethyl-piperidyl methacrylate,
tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane
tetracarboxylate,
tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butane
tetracarboxylate,
bis(2,2,6,6-tetramethyl-4-piperidyl).bis(tridecyl)-1,2,3,4-butane
tetracarboxylate,
bis(1,2,2,6,6-pentamethyl-4-piperidyl).bis(tridecyl)-1,2,3,4-butane
tetracarboxylate,
bis(1,2,2,6,6-pentamethyl-4-piperidyl)-2-butyl-2-(3,5-di-t-butyl-4-hydrox-
ybenzyl)malonate,
3,9-bis[1,1-dimethyl-2-[tris(2,2,6,6-tetramethyl-4-piperidyloxycarbonylox-
y)butylcarbonyloxy]ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane,
3,9-bis[1,1-dimethyl-2-[tris(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl-
oxy)butylcarbonyloxy]ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane,
1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane/2,4-dichloro-6-morpho-
lino-s-triazine polycondensate,
1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane/2,4-dichloro-6-t-octy-
lamino-s-triazine polycondensate,
1,5,8,12-tetrakis[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidypamino-
)-s-triazine-6-yl]-1,5,8,12-tetraazadodecane,
1,5,8,12-tetrakis[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)am-
ino)-s-triazine-6-yl]-1,5,8,12-tetraazadodecane,
1,6,11-tris[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino)-s-t-
riazine-6-ylamino]undecane,
1,6,11-tris[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidypamino)-s--
triazine-6-ylamino]undecane,
1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol/diethylsuccinate
polycondensate and
1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane/dibromoethane
polycondensate.
[0081] The amount of the above-described hindered amine-based light
stabilizer(s) to be blended is preferably 0.001 to 10 parts by mass
with respect to 100 parts by mass of the curable composition of the
present invention.
[0082] A flame retardant is an additive which imparts flame
retardancy to a resin. Examples thereof include phosphate compounds
such as triphenyl phosphate, phenol-resorcinol-phosphorus
oxychloride condensate, phenol-bisphenol A-phosphorus oxychloride
condensate and 2,6-xylenol-resorcinol-phosphorus oxychloride
condensate; phosphoric acid amide compounds such as
aniline-phosphorus oxychloride condensate and phenol-xylylene
diamine-phosphorus oxychloride condensate; phosphazenes;
halogen-based flame retardants such as decabromodiphenyl ether and
tetrabromobisphenol A; phosphates of nitrogen-containing organic
compounds, such as melamine phosphate, piperazine phosphate,
melamine pyrophosphate, piperazine pyrophosphate, melamine
polyphosphate and piperazine polyphosphate; red phosphorus and
surface-treated or microcapsulated red phosphorus; flame retardant
aids such as antimony oxide and zinc borate; and anti-drip agents
such as polytetrafluoroethylenes and silicon resins.
[0083] The amount of the flame retardant(s) to be blended is
preferably 2 to 20 parts by mass, more preferably 5 to 10 parts by
mass, with respect to 100 parts by mass of the curable composition
of the present invention.
[0084] A silane coupling agent is a component which improves the
adhesiveness of the resulting cured article. Examples thereof
include 3-chloropropyltrimethoxysilane, vinyltrichlorosilane,
vinyltriethoxysilane, vinyl-tris-(2-methoxyethoxy)silane,
3-methacryloxypropyltrimethoxysilane,
2-(3,4-ethoxycyclohexyl)ethyltrimethoxysilane,
3-glycidoxypropyltrimethoxysilane, vinyltriacetoxysilane,
3-mercaptopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane and
N-2-(aminoethyl)-3-aminopropyltrimethoxy silane.
[0085] The amount of the silane coupling agent(s) to be blended is
preferably 0.01 to 5 parts by mass, more preferably 0.1 to 2 parts
by mass, with respect to 100 parts by mass of the curable
composition of the present invention.
[0086] A mold-releasing agent is a component which improves the
mold-releasing from a die at the time of molding. Examples thereof
include carnauba wax, montanoic acid, higher fatty acids such as
stearic acid, metal salts of higher fatty acids, ester-based waxes
such as montanic acid ester, oxidized polyolefin-based waxes such
as oxidized polyethylene, and non-oxidized polyolefin-based waxes
such as non-oxidized polyethylene. These mold-releasing agents may
be used individually, or two or more thereof may be used in
combination. Among these mold-releasing agents, it is preferred to
use an oxidized polyolefin-based wax or a non-oxidized
polyolefin-based wax in an amount of 0.01 to 10 parts by mass, more
preferably 0.1 to 5 parts by mass, with respect to 100 parts by
mass of the curable composition of the present invention.
[0087] The curable composition of the present invention can be
cured by an active energy beam such as ultraviolet radiation,
electron beam, X-ray, radiation or high-frequency wave when a
photoradical generator is used as the component (B) or by heating
when a thermal radical generator is used as the component (B). It
is preferred that the curable composition of the present invention
be cured by heating since it has excellent molding processability
into a three-dimensional molded article. Various curing
temperatures can be set by selecting the type of the thermal
radical generator; however, when the curing temperature is
excessively low, the storage stability of the curable composition
of the present invention may become poor and there may arise a
problem in the workability due to an increase in the time required
for curing, while when the curing temperature is excessively high,
the dimensional accuracy of molding in the present invention may
become poor. Therefore, the curing temperature of the curable
composition of the present invention is preferably 100 to
250.degree. C., more preferably 150 to 200.degree. C.
[0088] The curable composition of the present invention can be
molded by a molding method known as a method of molding a
thermosetting resin, such as compression molding, transfer molding,
injection molding, extrusion molding, casting or RIM molding.
Thereamong, transfer molding is preferred since the curable
composition of the present invention has excellent molding
processability into a three-dimensional object. Further, the
curable composition of the present invention, after being cured,
may also be subjected to post-curing (after-curing) as required. By
performing post-curing, a curing reaction proceeds further, so that
the physical strength and heat resistance of the resulting cured
article of the curable composition of the present invention are
improved.
[0089] In cases where the curable composition of the present
invention is molded by transfer molding, the curable composition of
the present invention may be used as is; however, it is preferably
processed into a tablet before use since thereby air bubbles are
less likely to be entrapped and a good-quality cured article can be
obtained. In cases where the curable composition of the present
invention is processed into a tablet, the components of the curable
composition of the present invention may be loaded all together to
a dissolving bath and then melt-mixed batchwise, or the components
may be loaded all together to a kneader such as a heated 3-roll
mill and then melt-mixed continuously. The shape of the tablet is
not particularly restricted and it may be adjusted to the
specifications of the transfer molding machine in which the curable
composition of the present invention is used.
[0090] The curable composition of the present invention is
excellent in terms of molding processability, particularly molding
processability in transfer molding. The curable composition of the
present invention can thus be suitably used as a molding material
for a semiconductor element. Examples of a semiconductor element in
which the curable composition of the present invention is suitably
used include integrated circuits such as ICs and LSIs; optical
semiconductor elements such as light-emitting diodes (LEDs),
organic electroluminescent elements (organic ELs), laser diodes,
LED arrays and CCDs; and SiC power semiconductors. Since a cured
article of the curable composition of the present invention has
high heat resistance, it is particularly preferably used as a
molding material for a power semiconductor or power module where
high-level heat resistance is required, particularly as a molding
material for a SiC power semiconductor or SiC power module.
Examples of a power semiconductor in which the curable composition
of the present invention is used as a molding material include GTO
(Gate Turn Off) thyristors, insulated gate bipolar transistors
(IGBTs), metal oxide semiconductor field-effect transistors
(MOSFETs), static induction transistors (SITs), diodes, power
transistors, thyristors and triacs. Further, examples of a power
module include general-purpose inverter modules, IPMs (Intelligent
Power Modules) and inverter modules for automobiles. These power
semiconductors and power modules can be used in railcars, heavy
electric plants, hybrid cars, electric cars, robot welders,
elevators, air conditioners, uninterruptible power supplies (UPS),
general-purpose inverters (control units of general-purpose
motors), washing machines, microwave ovens, electromagnetic ranges,
electric fans, refrigerators, electric rice-cookers, VTRs, audio
instruments and the like.
[0091] In addition to the above, the curable composition of the
present invention can also be suitably used, for example, as an
insulating material of a semiconductor element and a substrate of a
printed circuit board or the like, as well as in the chassis and
parts of electrical products and electrical/electronic equipments
and parts of automobiles, railcars, airplanes and the like.
EXAMPLES
[0092] The present invention will now be described in more detail
by way of examples and comparative examples thereof. However, the
present invention is not restricted thereto by any means. It is
noted here that, in the following Examples, "part(s)" and "%" are
based on mass unless otherwise specified.
Production Example 1
Synthesis of Compound A1
[0093] To a glass reaction vessel equipped with an agitator, a
thermometer, a nitrogen-introducing tube, a dropping funnel and a
condenser tube, 549 g of 4,4'-(1-phenylethylidene)bisphenol (1.89
mol, manufactured by Honshu Chemical Industry Co., Ltd.), 1.4 kg of
methanol, 266 g (4.75 mol) of potassium hydroxide and 691 g (4.53
mol) of chloromethylstyrene were added and stirred at 60.degree. C.
for 1 hour. Then, after terminating the stirring, the resultant was
allowed to separate into two layers and the lower layer was
removed. The upper layer was cooled and purified by
recrystallization to obtain 613 g of a compound A1 as white solid
(yield: 62%). The thus obtained compound A1 had the following
structure and a melting point of 102.degree. C.
##STR00015##
Production Example 2
Synthesis of Compound A2
[0094] A compound A2 was obtained as white solid by performing the
same operations as in Production Example 1, except that
biphenyl-2,2'-diol was used in place of
4,4'-(1-phenylethylidene)bisphenol. The thus obtained compound A2
had the following structure and a melting point of 98.degree.
C.
##STR00016##
Production Example 3
Synthesis of Compound A3
[0095] A compound A3 was obtained as white solid by performing the
same operations as in Production Example 1, except that
1,6-naphthalene diol was used in place of
4,4'-(1-phenylethylidene)bisphenol. The thus obtained compound A3
had the following structure and a melting point of 122.degree.
C.
##STR00017##
Production Example 4
Synthesis of Compound A4
[0096] A compound A4 was obtained as white solid by performing the
same operations as in Production Example 1, except that
4,4'-dihydroxydiphenyl sulfide was used in place of
4,4'-(1-phenylethylidene)bisphenol. The thus obtained compound A4
had the following structure and a melting point of 170.degree.
C.
##STR00018##
Production Example 5
Synthesis of Compound A5
[0097] A compound A5 was obtained as white solid by performing the
same operations as in Production Example 1, except that
4,4'-dihydroxydiphenyl sulfone was used in place of
4,4'-(1-phenylethylidene)bisphenol. The thus obtained compound A5
had the following structure and a melting point of 121.degree.
C.
##STR00019##
Curable Resin Components for Comparison
[0098] a1: epoxy resin (manufactured by Sigma-Aldrich Co. LLC,
poly[(o-cresylglycidylether)-CO-formaldehyde], number-average
molecular weight (Mn): .about.870)
[0099] a2: phenol resin (manufactured by Gun Ei Chemical Industry
Co., Ltd., trade name: PSM4326)
Component (B)
[0100] B1: dicumyl peroxide (manufactured by NOF Corporation, trade
name: PERCUMYL D)
Component (C)
[0101] C1: triallyl isocyanurate (manufactured by Nippon Kasei
Chemical Company
Limited, trade name: TAIC)
Component (D)
[0102] D1: spherical silica (manufactured by Tokuyama Corporation,
trade name: SE-40, average particle size: 40 .mu.m)
[0103] D2: spherical silica (manufactured by Admatechs Company
Limited, trade name: SO-E5, average particle size: 15 .mu.m)
[0104] D3: molten silica (manufactured by DENKI KAGAKU KOGYO
KABUSHIKI KAISHA, trade name: FB-950, average particle size: 24
.mu.m)
Antioxidant
[0105] E1: 2,6-di-t-butyl phenol
[Tablet Preparation]
[0106] Using the thus obtained compounds A1 to A5 and the
above-described compounds, tablets having the respective
formulations shown in Table 1 and 2 were prepared by the following
steps. It is noted here that, in these Tables, all numerical values
are based on parts by mass.
(1) Melt-mixing the components other than the components (B) and
(D). (2) Using a mixer, knead the resulting mixture and the
components (B) and (D) at 100.degree. C. for 30 minutes. (3) Cool
and pulverize the kneaded product. (4) Using a tablet machine
(manufactured by Oji Kikai Co., Ltd., OTM-10-80), mold the
resultant into a tablet of 15 mm in diameter and 18 mm in height
(mass: about 25 g).
TABLE-US-00001 TABLE 1 Example 1 2 3 4 5 6 7 8 9 10 A1 100 100 100
100 100 50 -- 70 -- -- A2 -- -- -- -- -- 50 -- -- -- -- A3 -- -- --
-- -- -- 100 -- -- -- A4 -- -- -- -- -- -- -- 30 50 50 A5 -- -- --
-- -- -- -- -- 50 50 B1 1.1 0.7 2.2 1.1 1.1 1.1 1.1 1.1 1.1 0.6 C1
11 11 11 11 -- -- 11 11 11 11 D1 444 444 444 -- -- -- -- -- -- --
D2 185 185 185 -- -- -- -- -- -- -- D3 -- -- -- -- 604 604 604 604
604 604 E1 -- -- 0.3 0.3 0.3 0.3 0.3 0.3 0.3 --
TABLE-US-00002 TABLE 2 Comparative Example 1 2 3 4 5 6 A1 -- -- 100
100 100 -- A4 -- -- -- -- -- 50 A5 -- -- -- -- -- 50 a1 100 100 --
-- -- -- a2 36 36 -- -- -- -- B1 -- -- 0.1 0.4 0.3 0.3 C1 545 -- 11
11 -- 11 D1 227 -- 444 444 -- -- D2 -- 741 185 185 -- -- D3 -- --
-- -- 604 604 E1 -- -- -- -- 0.3 --
[Spiral Flow]
[0107] Using a transfer molding machine (manufactured by Kodaira
Seisakusho Co., Ltd., model: SP-T-10), the spiral flow length of
each tablet was measured under the following conditions. The
results thereof are shown in Table 3 and 4.
[0108] Die: spiral flow die (semicircular with a cross-sectional
radius of 2.5 mm)
[0109] Extrusion pressure: 10 MPa
[0110] Die temperature: 130.degree. C.
[0111] Injection time: 10 seconds
[Preparation of Test Piece]
[0112] Using a transfer molding machine (manufactured by Kodaira
Seisakusho Co., Ltd., model: SP-T-10), each tablet was
transfer-molded under the following conditions to prepare a test
piece of 100 mm in length, 35 mm in width and 2 mm in
thickness.
[0113] Injection Conditions
[0114] Extrusion pressure: 10 MPa
[0115] Die temperature: 130.degree. C.
[0116] Injection time: 2 minutes
[0117] Curing Conditions
[0118] Die temperature: 150.degree. C.
[0119] Curing time: 5 minutes
[0120] Post-curing
[0121] 250.degree. C., 30 minutes
[0122] Under the below-described conditions, the heat resistance
(residual weight ratio and bending modulus), linear thermal
expansion coefficient, glass transition temperature and 5% weight
reduction temperature were measured. The results thereof are shown
in Table 3 and 4.
[Heat Resistance]
[0123] The thus obtained test pieces were each stored under an
atmosphere in a 250.degree. C. oven for 100 hours and 300 hours.
Before the storage in the oven (0 hr), after 100 hours of storage
(100 hr) and after 300 hours of storage (300 hr), the residual
weight ratio and the bending modulus of each test piece were
measured by the below-described methods.
[Residual Weight Ratio]
[0124] The mass of each test piece was measured before the storage
in the oven, after 100 hours of storage and after 300 hours of
storage and it was expressed in percentage, taking the mass of each
test piece before the storage in the oven as 100%.
[Bending Modulus]
[0125] In accordance with JIS K6911 (Testing methods for
thermosetting plastics), the bending modulus was measured using a
resin universal tester (manufactured by SHIMADZU CORPORATION,
model: AUTOGRAPH AG-X).
[Linear Thermal Expansion Coefficient and Glass Transition
Temperature]
[0126] Using a thermomechanical analyzer (manufactured by SII
NanoTechnology Inc., model: EXSTAR TMA/SS 6100), the linear thermal
expansion coefficient and the glass transition temperature were
measured.
[5% Weight Reduction Temperature]
[0127] After collecting 1 part of each test piece, the 5% weight
reduction temperature thereof was measured under the following
conditions using a differential thermogravimetric simultaneous
measurement apparatus (manufactured by SII NanoTechnology Inc.,
model: EXSTAR TG/DTA 6300).
[0128] Measurement atmosphere: in the air
[0129] Initial heating temperature: 100.degree. C.
[0130] Heating rate: 10.degree. C./minute
[0131] Final heating temperature: 550.degree. C.
TABLE-US-00003 TABLE 3 Example 1 2 3 4 5 6 7 8 9 10 Spiral flow
(cm) 104 104 103 >150 >150 >150 98 90 110 110 Glass
transition temperature >300 >300 >300 >300 >300
>300 >300 >300 >300 >300 (.degree. C.) Linear
thermal .alpha.1*.sup.1 11 11 11 75 11 16 15 15 14 14 expansion
coefficient .alpha.2*.sup.2 -- -- -- -- -- -- -- -- -- -- (ppm/K)
5% weight reduction 490 492 485 425 458 515 527 513 519 519
temperature (.degree. C.) Heat Residual 0 hr 100 100 100 100 100
100 100 100 100 100 resistance weight 100 hr 99.9 99.9 99.9 98.8
99.9 99.9 99.9 99.9 99.9 99.9 (%) 300 hr 99.7 99.8 99.5 98.0 99.8
99.7 99.7 99.7 99.8 99.8 Bending 0 hr 26 26 26 3.5 25 26 28 27 24
24 modulus 100 hr 27 27 27 3.5 26 26 28 28 24 24 (GPa) 300 hr 28 28
29 3.5 26 28 29 29 25 25 *.sup.1.alpha.1 = Linear thermal expansion
coefficient before reaching the glass transition temperature
*.sup.2.alpha.2 = Linear thermal expansion coefficient after
reaching the glass transition temperature
TABLE-US-00004 TABLE 4 Comparative Example 1 2 3 4 5 6 Spiral flow
(cm) 100 >150 104 104 >150 110 Glass transition temperature
(.degree. C.) 124 126 208 221 218 229 Linear thermal expansion
.alpha.1*.sup.1 18 19 12 12 76 15 coefficient (ppm/K)
.alpha.2*.sup.2 61 64 54 53 109 55 5% weight reduction temperature
(.degree. C.) 459 455 482 485 412 488 Heat Residual weight 0 hr 100
100 100 100 100 100 resistance (%) 100 hr 99.5 99.4 99.8 99.8 98.8
99.9 300 hr 98.7 98.5 99.5 99.6 98.0 99.8 Bending 0 hr 21 20 24 25
3.5 24 modulus 100 hr 21 20 25 26 3.5 24 (GPa) 300 hr 15 14 27 27
3.5 25 *.sup.1.alpha.1 = Linear thermal expansion coefficient
before reaching the glass transition temperature *.sup.2.alpha.2 =
Linear thermal expansion coefficient after reaching the glass
transition temperature
[0132] As clearly seen from Table 3, it was confirmed that the
cured articles of the curable composition according to the present
invention had a spiral flow equal to or higher than those of the
comparative epoxy resin compositions and thus had a higher fluidity
at the time of heat molding as well as superior productivity. In
addition, the cured articles according to the present invention had
a high residual weight ratio, a low linear expansion coefficient
and a high glass transition temperature. From comparisons between
Example 4 and other Examples, it was revealed that, by
incorporating a filler into the curable composition of the present
invention, the linear thermal expansion coefficient and the heat
resistance are markedly improved. The cured articles of the present
inventions have a glass transition temperature of 300.degree. C. or
higher; therefore, they can also be suitably used in SiC power
semiconductors that may possibly be used at a high temperature of
about 300.degree. C. On the other hand, as clearly seen from the
results of Comparative Examples 1, 2 and 3 to 6, a sufficient glass
transition temperature was not attained in conventional epoxy resin
compositions and those curable compositions in which the component
(A) according to the present invention was used but the amount of
the component (B) was less than a prescribed value.
* * * * *